The rate coefficient (k₁) for the reaction of OH radicals with perfluoro ethyl vinyl ether (PEVE, C₂F₅OCFCF₂) has been measured as a function of temperature (T = 207–300 K) using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence (PLP-LIF) at pressures of 50 or 100 Torr N₂ bath gas. In addition, the rate coefficient was measured at 298 K and in one atmosphere of air by the relative-rate technique with loss of PEVE and reference reactant monitored in situ by IR absorption spectroscopy. The rate coefficient has a negative temperature dependence which can be parameterized as: k₁(T) = 6.0 × 10⁻¹³ exp[(480 ± 38/T)] cm³ molecule⁻¹ s⁻¹ and a room temperature value of k₁ (298 K) = (3.0 ± 0.3) × 10⁻¹² cm³ molecule⁻¹ s⁻¹. Highly accurate rate coefficients from the PLP-LIF experiments were achieved by optical on-line measurements of PEVE and by performing the measurements at two different apparatuses. The large rate coefficient and the temperature dependence indicate that the reaction proceeds via OH addition to the CC double bond, the high pressure limit already being reached at 50 Torr N₂. Based on the rate coefficient and average OH levels, the atmospheric lifetime of PEVE was estimated to be a few days.

中文翻译：

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全氟乙基乙烯基醚（C ₂ F ₅ OCF CF ₂）与OH 反应的速率系数的绝对和相对速率测量

使用脉冲技术测量了OH自由基与全氟乙基乙烯基醚（PEVE，C ₂ F ₅ OCF CF ₂）反应的速率系数（k ₁）与温度的关系（T = 207–300 K）。激光光解，在50或100 Torr N ₂浴气体压力下通过激光诱导荧光（PLP-LIF）检测OH 。此外，通过相对速率技术在298 K的空气中和一个大气中测量速率系数，并通过IR吸收光谱法对PEVE的损失和参考反应物进行了现场监测。速率系数具有负温度依赖性，可以将其参数化为：k₁（ T）= 6.0×10 ^-13  exp [（480±38 / T）] cm ³分子^-1 s ^-1和室温值k ₁（298 K）=（3.0±0.3）×10 ^-12 cm ³分子^-1 s ^-1。通过对PEVE进行光学在线测量并在两个不同的设备上进行测量，可以从PLP-LIF实验获得高精度的速率系数。较大的速率系数和温度依赖性表明反应是通过向C中添加OH来进行的C双键，高压极限已达到50 Torr N ₂。根据速率系数和平均OH含量，估计PEVE在大气中的寿命为几天。